Study Guide 1 Flashcards

(71 cards)

1
Q

What are the different types of corrosion? (8)

A
Galvanic Corrosion
Crevice Corrosion
Pitting Corrosion
Intergranular Corrosion
Stress \& Galvanic Corrosion
Stress Corrosion
Fatigue Corrosion
Fretting Corrosion
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2
Q

Galvanic Corrosion

A

Corrosion that mimics what occurs in a half cell.

2 metals: Zn & Cu are electrically coupled where electrons can transfer btw metals - like a wire.

Physiological fluid acts as a “salt bridge”.

*Note: If a stainless steal is coupled with another metal, it will undergo “anodic dissolution”.

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3
Q

Crevice Corrosion

A

Occurs in areas with a narrow, deep crack.

Usually btw screw & plate of bone fixation device.

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4
Q

Pitting Corrosion

A

Small flaw/disruption in passivation film.

Usually difficult to detect & leads to device failure.

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5
Q

Intergranular Corrosion

A

Grain boundaries are energetically active.

more active = anodic regions

(e.g. Occurs in stainless steel at the grain boundaries due to depletion of Cr; where Cr is required for passivating layer)

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6
Q

Stress & Galvanic Corrosion

A

Bending of a metal;
tensile side = anodic
compressive side = cathodic

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7
Q

Stress Corrosion Cracking

A

Occurs to a metal under tension in corrosive environment.

Cracks are often perpendicular to applied stress.

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8
Q

Fatigue Corrosion

A

Perturbing the passivating film around the implant via cyclic loading.

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9
Q

Fretting Corrosion

A

Motion disrupts the passivating layer.

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10
Q

Why does biological protein adsorption disrupt the formation of a passivating layer on a metal implant?

A

Biological proteins adsorb to the surface to:

a. Create a barrier that reduces O2 diffusion to the surface - which in turn disrupts the formation of the oxide passivation layer
b. Proteins can accept electrons from metals and the rxn is shifted towards the metal being dissolved.
* Note: Inflammatory cells can use a drop in pH to release strong oxidizing agents = increasing the passive layer.

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11
Q

Corrosion Control

A

Reduce the number of stress raisers in design.

Reduce galvanic corrosion by choosing metals which are close to each other in the galvanic series.

Choose cahtodic metals: Au, Ag, Pt; which are usually ductile & expensive

Choose metals that form passive layers. (e.g. alone/alloys)

Reduce intergranular corrosion by the heat treatment of stainless steel (why?)

Create passive layer prior implantation via “pre-treatment w/ nitric oxide”

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12
Q

Ceramic Degradation

A
metal = corrosion
ceramic/polymer = degradation

Ceramics (FeO2) = passive layer around metals

Ceramics are usually more stable than metals, but require more energy to separate ionic bonds.

Ceramics = inert, resorbable, have controlled surface reactivity.

Ceramics undergo stress-induced degradation = brittle

Ceramic porosity = degradation
(e.g. pores create more SA for degradation & are also stress raisers = lead to more cracks)

*Need to a balance btw porosity and degradation.

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13
Q

Polymer Degradation

A

Degradation usually leads to discoloration, appearance of cracking (e.g. crazing), and change in mechanical properties.

This can occur via water, proteins, inflammatory cells, and mechanical stress.

2 Mechanisms: Swelling/Dissolution and Polymer Scission

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14
Q

Mechanisms of Polymer Degradation (2)

A

Swelling/Dissolution:
If polymer has hydrophilic domains, H2O disrupts 2ndary bonding btw polymer chains.

affects polymer crystallinity = affects mechanical & thermal properties

Polymer may dissolve completely due to solubility & number of covalent bonds btw polymer chains.

Polymer Scission:
Breaking of the primary bonds of polymer.

Decreases Mw = affect mechanical properties and Tg

Occurs via Hydrolysis & RedOx Rxns

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15
Q

Chain Scission via Hydrolysis

A

Typical degradation process in condensation polymers.

Depends on:

Reactivity of groups in the polymer backbone.

Interchain bonding.

Amount of media available to the polymer.

Number of cleavable groups and hydrophilic domains

Low/No crystallinity

Low Mw & low crosslink density polymers = hydrolysis

High SA to V ratio

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16
Q

Chain Scission via Oxidation

A

Free radicals (highly reactive species) break down covalent bonds via 3 processes:

  1. Initation: Loss of H+ from chain = highly reactive R-group
  2. Propogation: R-group interacts with O2 to form radical ROO- = accepts H+ from another part of chain
  3. Termination: Combining free radicals to create inert products
    * Note: Oxidation usually caused by agents released by inflammatory cells. If a metal is complexed w/ a polymer, the polymer can break down & corrosion of the metal can lead to the oxidation of a polymer – Metal-catalyzed Oxidation.
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17
Q

Other forms of Polymer Degradation (2)

A

Environmental Stress Cracking: Subjected to tensile stress, and crack develops perpendicular to loading axis. (e.g. similar to stress corrosion cracking in metals; usually inflammatory cells are required for this type of cracking to occur.)

Enzyme-Catalyzed Degradation:
Lowers the energy required for hydrolysis/oxidation, enzymes break down natural/synthetic polymers. Usually occurs quickly in porous polymers.

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18
Q

Bulk Erosion & Surface Erosion

A

Bulk Erosion: change of shape/size of polymer w/in its core

Surface Erosion: change of shape/size of polymer upon its surface

*Note: Degradation = breaking of chemical bonds.

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19
Q

What’s the difference btw natural and synthetic polymers?

A

Synthetic: Degrade by hydrolysis/enzymes

Natural: Degrade by enzymes (depending on the material)

*Note: Hydrolysis Breakdown - Bulk/Surface Degradation.

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20
Q

Hydrolysis Breakdown (2)

A

Bulk Degradation: Rate of H2O into a polymer > the rate the polymer is converted to its water-soluble degradation products.

Surface Degradation:
The rate of H2O penetrates into the material

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21
Q

Biodegradable Ceramics

A

Typically degrade by erosison, but is influenced by:

Chemical susceptibility of material.

Amount of crystallinity.

Amount of H2O available.

SA to V ratio.

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22
Q

What are some tests use for measuring degradation?

A

In vivo testing

In vitro testing

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23
Q

What is a bioactive factor?

A

A factor that stimulates a cell.

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24
Q

Facilitated Degradation

A

Body provides neurtal pH & constant temp.

Ions in the blood initiate corrosion. (e.g. K+, Ca2+, Na+)

Inflammatory cells can attach to the biomaterial surface and release oxidizing agents (e.g. peroxides) and lower the pH in that area.

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25
RedOx Rxns
LEO says GER anode = oxidation = dissolved = increasingly active (e.g. Zn) cathode = reduction = expanded = increasingly inert (e.g. Cu)
26
What is an electrochemical galvanic cell?
A battery. Components: Electrodes - Metal strips of Zn & Cu Salt Bridge - KCl which provides ions to maintain neutral charge *Note: Each metal is compared to a H+ electrode to rank oxidation behavior = STD Reduction Potentials. (e.g. metals with more (-) STD RP will always act as anode.)
27
Galvanic Series
Data of corrosive properties of metals in sea water. Metals at the bottom of the list are more easily oxidized (creating electrons) than those at the top = anodic (e.g. Mn)
28
Nernst Equation
Depends on the temperature and concentration of ions. E1: M1 --> M1+ + ne E2: M2+ ne --> M2 where electrochemical potential for the entire cell is: deltaE = (E2 - E1) DE0 = (E20 – E10) – RT/nF ln ([M1n+]/[M2n+]) R - gas const in mol T - temp in K F - Faraday's const in Coulombs n - number of valence e transferred
29
Pourbaix Diagram
Focuses on cell potential and pH. Divided into 3 main regions: 1. Corrosion: >> 10^-6M of metal ions are found in soln. 2. Immunity: not energetically favorable for the metal to corrode, metal cannot act as anode. 3. Passivation: surface oxidation leads to stable film formation; coating the metals using oxides/hydroxides. Corrosion can be stopped because of this film. (e.g. passivation films = Cr, Fe, Ni, Ti, Al)
30
Factors Affecting Corrosion
Metal Processing/Handling Techniques Mechanical Loading Presence of Proteins, Cells and Bacteria Microstructure (cracks) can alter the local on concentration. Implant Corrosion: ions leach out of metal into surrounding biological tissue causing alterations/mutations
31
Quantifying Ductility
% Elongation = (lf-lo)/lo x 100 % Area Reduction = (Ao - Af)/Ao x 100
32
Semicrystalline Polymers
Focused on highly crystalline materials. In tensile situations, once the "neck" region forms, it continues to extend. Just before fracture, the stress increases dramatically.
33
True Stress/Strain
Stress = F/Ain Strain = ln ( Li/Lo)
34
How can we improve mechanical properties?
Reduce the movement of dislocations. Adding elements to material to reduce slip Create alloys. Additional metals can cancel lattice strain in other regions of the material. Increase grain boundaries per volume = stronger Polycrystalline >> one crystal Fillers within POLYMERS can add additional CROSSLINKS that add strength to a material.
35
Mechanical Testing: Creep
Plastic deformation of a sample under constant load (tensile) over time while maintaining the system at a fixed temp. Strain is recorded over time. Considered for: 1. Temps > 0.4Tm for metals 2. Temps > 0.4Tm for ceramics 3. Creep occurs @ Room Temp (above Tg)
36
Stages of Creep
Primary Creep: Increase in strain w/time, creep rate decreases and a minimum creep rate is found. Secondary Creep: Linear relationship btw creep strain and time. Tertiary Creep: leads to failure. *Note: assesses the mechanical properties of polymers
37
Stress Relaxation
Specimen is loaded w/ sufficient stress to produce a small strain. The changes in stress need to maintain a const. strain Speciment is maintain at const temp. *Note: assesses the mechanical properties of polymers.
38
Viscoelastic Materials
Materials w/ Tg and Tm (polymeric) which have viscous and elastic properties. Above Tm = Viscous Below Tg = Elastic (e.g. Maxwell & Voigt Model)
39
How does porosity effect the mechanical properties of materials?
Pores decrease the elastic modulus & strength of material. Pores decrease cross-sectional area where sample is loaded. Pores can act as stress concenrators/raisers Essentailly, materials become weaker.
40
Fracture
Ductile: plastic deformation before breaking Brittle: very little plastic deformation before breaking
41
Fatigue Testing
Examining how biomaterials behave under repeated loading. Fatigue Fracture: 90% of metallic failures Crack Initiation Crack Propogation: crack increases in size Final Failure: crack limit size is reached.
42
How do materials fatigue more quickly?
1. Increasing Stress 2. Defects/Impurities at the surface 3. Reducing Notches/Sharp Edges 4. Implant Environment - Corrosion/Chemical attack
43
Mechanical Testing Analysis
Components: 1. Grips = hold sample 2. Load cell = records forces 3. Extensometer = measures length 4. Processor = converts electrical signals to stress/strain plot
44
Tensile Testing
Force perpendicular to the area that is used to pull the material apart. Measures load and elongation.
45
Compression Testing
Force is negative (opposite direction) = stress is negative Lo > Li = strain is negative
46
Hooke's Law
E = Stress / Strain Stress = E x Strain
47
Shear Stress
Forces are parallel to top and bottom faces of sample Equation: Tau = F/Ao Shear Strain Equation: Gamma = tan(theta) theta = angle of deformation
48
Yield Strength
Stress @ the end of the elastic region of the stress/strain curve
49
Yield Point Strain
The corresponding strain @ Yield Strength
50
Ultimate Tensile Strength
After yielding, continuing plastic deformation until maximum stress is reached = necking occurs.
51
Why are voids important?
Provides more space for nutrient and waste to through in & out of the biomaterial. Provides more surface volume for cells to attach to. More pores = weaker material
52
Polymer Crystallinity
Depends on: -mer side groups (e.g. large and bulky = less crystalline) Chain branching (e.g. more branching = less crystallinity) Tacticity (e.g. atatic polymers = less crystalline than isotatic and syndiotatic) Regularity of -mer placement in copolymers.
53
Thermal Transitions
Body = 37 degree celcius Tm Tg
54
Melting Point (Tm)
Temperature at which energy is high enough to break the material's ordered structure. Above Tm = liquid Below Tm = solid Increases Mw b/c chain ends require less energy to move. More branching = not tightly packed = less energy to move *Note: There are no exact Tm for amorphous (glass) ceramics and polymers.
55
Amorphous Glasses
No exact Tm. Have a working point = temp at which viscocity of glass is 10^4 P
56
Viscosity
The rate at which a liquid resists shear and tensile stress.
57
Glass Transition Temperate (Tg)
The temp below the material is considered a glass.
58
What are the factors that influence Tg?
Chain flexibility (e.g. C-O bonds (lower Tg) are more flexible than C-C bonds.) Bulky side groups = impede motion = increase Tg Polar side groups = promote chain interactions = increase Tg Crosslinking (linking polymer to another) = increase Tg
59
Differential Scanning Calorimetry (DSC)
Tells you what Tm and Tg are.
60
Polymer Configuration
Isotatic - R group same side Syndiotatic - R group opposite Atatic - R group random
61
Polymer Synthesis
Addition (adding polymers) and Condensation (H2O is lost) Initation (attach R group), Propogation (crosslink), Termination (end w/ R group)
62
Copolymers
Two distinct chemical structures crosslink. Random Copolymer Alternating Copolymer Block Copolymer Graft Copolymers = desirable chemical characteristics (e.g PLGA)
63
X-ray Diffraction
X-rays > photons > biomaterial surface atoms in biomaterial > scatter X-rays X-ray detectors > get reflected X-ray patterns for specific chemicals *Good for: size of unit cell/geometry & compound identification ``` Contents: X-ray source Sample Holder Counter PC ```
64
UV-VIS Spectroscopy
energy > UV light > specimen e inside specimen excited > higher level e > returns to normal state > energy released chemical structures absorb energy differently *Good for: identifies samples/chemical groups, concentration of specific molecules in a material ``` Components: Source Wavelength Selection Detector PC ```
65
IR Spectroscopy
bonds btw atoms move = frequency if energy onto bonds = same frequency = oscillations increase *Good for: amounts of substances, characterizes biomaterials; elements should have permanent dipole!!!! ``` Components: IR Source Wavelength Selector Detector Processor ```
66
Mass Spectroscopy
Sample is ionized > exposed to e> forced into magnetic field > heavy/light = different deflection *Good for: analyzes synthetic/natural polymers, isotope ratios, determines Mw of materials ``` Components: Ionizing Chamber Mass Analyzer Detector PC ```
67
Size Exclusion Chromotography (SEC)
HPLC - separation of substances based on chemical properties like size and charge. SEC - determines Mw of polymers separation occurs based on pores particles can see > small molecules interact w/ more pores large molecules elute first, small molecules elute last ``` Components of SEC: (Filtration by size concept) Two Phases: Mobile/Stationary Mobile Phase: liquid solvent Stationary Phase: silica beads Gel Filtration: aqueous - mobile Gel Permeation: hydropobic - stationary ```
68
Schottky Defect
Vacancy of both anion and cation.
69
Frenkel Defect
vacancy/interstitial pair is create to maintain electroneutrality
70
Polydispersity Index (PI)
PI = Mw/Mn
71
Diffusion
Number of atoms diffusion through a cross-sectional area per time.